CN102229701B - Non-ionic aqueous epoxy resin emulsion and its preparation method - Google Patents

Abstract

The invention relates to the technical field of chemical coatings, in particular to a non-ionic water-based epoxy resin emulsion and a preparation method thereof. A non-ionic water-based epoxy resin emulsion of the present invention first dissolves a monoaminopolyether solution dissolved in an organic solvent Slowly add it dropwise to the mixture of epoxy resin and polyol glycidyl ether to react at 90°C to 160°C to generate an epoxy-terminated intermediate product, that is, an epoxy resin emulsifier. Then mix epoxy resin, epoxy diluent and epoxy resin emulsifier at 40°C-50°C, slowly add deionized water dropwise under high-speed shearing, and obtain a stable water-based epoxy resin by phase inversion method lotion. The epoxy resin emulsion of the invention has small particle size and high stability; in addition, the cured coating film of the emulsion has excellent performance and simple production process. The water-based epoxy emulsion of the present invention can be applicable to aspects such as water-based paints and water-based adhesives, such as floor paints, industrial protective paints, and the like.

Description

A kind of nonionic water-based epoxy resin emulsion and preparation method thereof

technical field

The invention relates to the technical field of chemical coatings, in particular to a nonionic water-based epoxy resin emulsion and a preparation method thereof.

Background technique

Traditional epoxy resin coatings have the advantages of high adhesion, good wear resistance, and excellent chemical and solvent resistance. As a primer, they can be applied to almost all material surfaces, and are widely used in the manufacture of industrial anti-corrosion coatings and food packaging. Coatings, electrophoretic coatings and powder coatings, etc. As people's requirements for environmental protection become increasingly urgent and strict, the development of low-VOC (volatile organic compound) waterborne epoxy resin systems and related coating products has become a new research direction.

Chinese invention patent (publication number CN 101117377A) discloses a kind of preparation method of water-based epoxy resin, and the method is: (1) in bisphenol A type epoxy resin, drop a certain ratio of auxiliary solvent I and II, stir Uniformly dissolves the resin completely. (2) (1) The product is reacted with polyol amine to prepare modified epoxy resin. After the reaction is completed, vacuumize to remove the solvent, and preheat for a period of time to reduce the viscosity of the modified epoxy resin. (3) Slowly add an organic acid dropwise to the product prepared in (2) to neutralize and form a salt. (4) Add a certain amount of water to the product of (3) to obtain a modified epoxy resin water-based system. This method increases its hydrophilicity by neutralizing organic acids to form salts, but the presence of organic acids will easily cause flash rust on the metal body; in addition, due to the addition of organic acids, when used together with some basic pigments and fillers , will have a certain impact on the stability of the coating.

Chinese invention patent (publication number CN 1911920A) discloses a 2-aminoethanesulfonic acid modified water-based epoxy resin and a preparation method thereof. The water-based epoxy resin consists of 100 parts by mass of epoxy resin, 2-amino It is obtained by mixing 3-50 parts of ethanesulfonic acid, 10-50 parts of water and 0.3-5 parts of surfactant, and then copolymerizing at 80-85°C. This method needs alkalis such as sodium hydroxide to be neutralized to form a salt, and the water resistance is not good, and the surfactant used in this method is a non-reactive surfactant, which does not participate in curing and forming a film, and is easily washed away by water. Free in the medium, affecting the appearance and anti-corrosion performance of the coating film.

Chinese invention patent (publication number CN 101177479A) discloses a kind of preparation method of self-emulsifying aqueous epoxy resin emulsion. In this method, polypolyol glycidyl ether and polyethylene glycol monoether are respectively introduced into the main chain and side chain of the epoxy resin by means of extended chain grafting reaction to increase its hydrophilicity to make water-based epoxy resin, and finally add water, Aqueous epoxy resin emulsion was obtained by self-emulsification reaction. However, the reaction of this method is more complicated, the operation is more cumbersome, and the cost is higher.

U.S. Patent No. 5,602,193 uses carboxyl-terminated polyether and epoxy resin to introduce hydrophilic groups through esterification, and then adds epoxy diluent and deionized water to prepare water-based epoxy resin emulsion. The epoxy resin emulsion prepared by this method has poor stability, and the lipids are easily hydrolyzed.

USP6271287 adopts low-temperature nonionic surfactant, high-temperature nonionic surfactant and anionic surfactant to react with epoxy resin to prepare epoxy resin dispersion with small particle size and high storage stability. However, the preparation method is extremely cumbersome, which is not conducive to large-scale production.

Contents of the invention

Aiming at the above-mentioned deficiencies in the prior art, the present invention adopts the reaction of epoxy resin with monoamino polyether and polypolyol glycidyl ether to prepare epoxy resin emulsifier, and then emulsifies the technical route of epoxy resin with the emulsifier, the specific process As shown in Figure 1, a nonionic water-based epoxy resin emulsion and a preparation method thereof are provided.

The present invention is achieved through the following technical solutions:

The invention provides a nonionic water-based epoxy resin emulsion, which is composed of the following components in mass percent:

Epoxy resin 25%～40%,

Epoxy resin emulsifier 13%～20%,

Deionized water 35%～55%,

Epoxy diluent 1%～12%,

Epoxy resin emulsifier described wherein is made up of the component of following mass percentage content:

Epoxy resin 15%～30%,

Monoamino polyether 25%～60%,

Polypolyol glycidyl ether 15% to 30%,

Organic solvent 5%～20%,

The epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin or novolac epoxy resin, wherein the epoxy value is 0.1-0.6;

The average molecular weight of the monoamino polyether is 500-5000;

The average molecular weight of the polypolyol glycidyl ether is 200-10000.

The monoamino polyether is one or more of M-600, M-1000, M-2070 series.

The polypolyol glycidyl ether is one of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or polypropylene glycol triglycidyl ether.

The epoxy diluent is a kind of butyl glycidyl ether, octyl glycidyl ether, alkyl glycidyl ether of carbon twelve to fourteen, phenyl glycidyl ether or trimethylol propane triglycidyl ether or several.

The organic solvent is one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether or ethylene glycol butyl ether.

The present invention also provides a kind of preparation method of nonionic waterborne epoxy resin emulsion, and concrete steps are:

(1) Preparation of epoxy resin emulsifier: In the reaction device, add the epoxy resin and polypolyol glycidyl ether in the stated proportion, raise the temperature to 90°C to 160°C, and then add dropwise the stated proportion dissolved in the organic solvent Monoamino polyether solution, continue to react at constant temperature for 2h ~ 5h, after the reaction is completed, keep in airtight;

(2) Preparation of water-based epoxy resin emulsion: mix the epoxy resin emulsifier, epoxy resin, and epoxy diluent prepared in (1) evenly according to the stated ratio, heat to 40°C to 50°C, and Slowly add the deionized water in the said ratio dropwise, and stir for 10-30 minutes after the phase inversion occurs, to obtain a non-ionic water-based epoxy resin emulsion.

Compared with the prior art, the present invention has the following advantages:

(1) The present invention prepares reactive epoxy resin emulsifier with epoxy resin, monoamino polyether, polypolyol glycidyl ether mixed reaction, introduces the affinity of monoamino polyether and polypolyol glycidyl ether simultaneously Water chain segment, the emulsifier has dual functions of emulsifying epoxy resin and participating in curing and film formation.

(2) The present invention adopts the reaction of epoxy group and amino compound to prepare emulsifier, the reaction is easy to carry out, no catalyst is needed, and it is beneficial to reduce the cost.

(3) The water-based epoxy resin emulsion of the present invention has low viscosity, small particle size, good storage stability, no delamination when stored at 50°C for 1 month, and no delamination, sedimentation, and low viscosity when stored at room temperature for 6 months. No significant change.

(4) The present invention also has the characteristics of simple preparation process.

Description of drawings

Fig. 1 is the preparation flow chart of aqueous epoxy resin emulsion of the present invention.

Figure 2 is a particle size distribution diagram of an aqueous epoxy resin emulsion.

Fig. 3 is the electrochemical impedance spectrum EIS figure of waterborne epoxy resin coating film.

Detailed ways

In order to better understand the present invention, the present invention will be further described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited to the range indicated by the examples.

Example 1

Prepare raw materials according to the following components and their mass percentages in the total materials:

Component Mass % (wt.%)

E-51 40%,

Epoxy resin emulsifier 13%,

Deionized water 37%,

Trimethylolpropane Triglycidyl Ether 10%,

Wherein said epoxy resin emulsifier component and component mass percent content are as follows:

E-51 18%,

M-2070 57%,

Polyethylene glycol diglycidyl ether 15%,

Propylene Glycol Methyl Ether 10%,

In a reactor equipped with reflux, heating and stirring devices, add epoxy resin E-51 and polyethylene glycol diglycidyl ether, mix well, raise the temperature to 120 ° C, and then slowly drop M- 2070 solution (about 1h after dripping), continue to react at constant temperature for 2h, and obtain a slightly yellow epoxy resin emulsifier.

Mix the above-prepared epoxy resin emulsifier, epoxy resin E-51, and trimethylolpropane triglycidyl ether evenly, heat to 40-50°C, slowly add deionized water dropwise under high-speed shearing, and wait until Stir for 15 minutes after inversion of the phase to obtain a milky white non-ionic water-based epoxy resin emulsion with a solid content of 50%, a viscosity of 400 mPa·s, an epoxy value of 0.2, and a particle size of 260 nm.

A kind of water-based epoxy resin emulsion prepared by the present example has a smaller particle size, shown in accompanying drawing 2 is the particle size distribution figure of the water-based epoxy emulsion of the present invention, as can be seen from Figure 2, the average particle size is 260nm, illustrating the present invention The particle size of the water-based epoxy resin emulsion is small, which is conducive to the film-forming reaction with the water-based epoxy resin curing agent.

The use of this epoxy resin emulsion:

Component A: This epoxy resin emulsion Component B: BECKOPOX VEH 2188w/55wa

Mix component A: component B = 1.1:1 (equivalent ratio), mix and stir evenly, and apply it on the pre-polished test panel. After the water evaporates, a transparent coating film is formed. The main properties of the coating film are shown in Table 1:

Table 1 embodiment 1 water-based epoxy resin emulsion coating film performance after curing

A kind of water-based epoxy resin emulsion prepared in this example can be applied to anti-corrosion coatings. Accompanying drawing 3 shows the electrochemical impedance spectrum EIS figure of the water-based epoxy resin coating film of the present invention. The test adopts a three-electrode system, the saturated calomel electrode with a capillary is used as the reference electrode, the platinum sheet is used as the counter electrode, and the coated (thickness 80 μm) carbon steel substrate is used as the working electrode; the corrosion medium is sodium chloride with a mass fraction of 3.5% Solution; test time After soaking for 3 hours, at the open circuit point, the amplitude of the sine wave excitation signal is 20mV, and the scanning frequency range is 100kHz to 10MHz. As can be seen from Fig. 3, the coating film ion permeation resistance value that water-based epoxy emulsion of the present invention forms is (10) ^7.6 , shows that this coating film has good corrosion resistance, illustrates that water-based epoxy resin emulsion of the present invention can be applicable to anti-corrosion corrosion paint.

Example 2

Prepare raw materials according to the following components and their mass percentages in the total materials:

Component mass percentage (wt.%)

E-44 34%,

Epoxy emulsifier 16%,

Deionized water 45%,

Octyl Glycidyl Ether 5%,

Wherein said epoxy resin emulsifier component and component mass percent content are as follows:

E-44 23%,

M-600 25%,

M-2070 20%,

Polypropylene Glycol Diglycidyl Ether 20%,

Propylene Glycol Butyl Ether 12%,

In the reactor equipped with reflux, heating and stirring devices, add epoxy resin E-44 and polypropylene glycol diglycidyl ether, mix well, raise the temperature to 125°C, and then slowly add M-600 dissolved in propylene glycol butyl ether dropwise, M-2070 solution (about 1.5h after dripping), continue to react at constant temperature for 3h, and obtain a slightly yellow epoxy resin emulsifier.

Mix the epoxy resin emulsifier, epoxy resin E-44, and octyl glycidyl ether prepared above evenly, heat to 40-50°C, slowly add deionized water dropwise under high-speed shear, and stir after the phase inversion occurs After 10 minutes, a milky white non-ionic water-based epoxy resin emulsion was obtained, with a solid content of 54%, a viscosity of 500 mPa·s, an epoxy value of 0.15, and a particle size of 340 nm.

The use of this epoxy resin emulsion:

Component A: This epoxy resin emulsion Component B: BECKOPOX VEH 2188w/55wa

Mix component A: component B = 1:1 (equivalent ratio), mix and stir evenly, and apply it on the pre-polished test panel. After the water evaporates, a transparent coating film is formed. The main properties of the coating film are shown in Table 2:

Table 2 Example 2 The coating performance of the aqueous epoxy resin emulsion after curing

Example 3

Prepare raw materials according to the following components and their mass percentages in the total materials:

Component Mass % (wt.%)

E-51 25%,

Epoxy resin emulsifier 20%,

Deionized water 50%,

Phenyl glycidyl ether 5%,

Wherein said epoxy resin emulsifier component and component mass percent content are as follows:

E-51 30%,

M-1000 12%,

M-2070 15%,

Polypropylene Glycol Triglycidyl Ether 30%,

Propylene Glycol Methyl Ether 13%,

In the reaction device equipped with reflux, heating and stirring devices, add epoxy resin E-51 and polypropylene glycol triglycidyl ether, mix well, raise the temperature to 130°C, and then slowly add M-1000 dissolved in propylene glycol methyl ether dropwise, M-2070 solution (after about 1 hour of dripping), continue to react at constant temperature for 2.5 hours to obtain a slightly yellow epoxy resin emulsifier.

Mix the epoxy resin emulsifier, epoxy resin E-51, and phenyl glycidyl ether prepared above evenly, heat to 40-50°C, slowly add deionized water dropwise under high-speed shear, and stir after the phase inversion occurs After 20 minutes, a milky white non-ionic water-based epoxy resin emulsion was obtained, with a solid content of 50%, a viscosity of 210 mPa·s, an epoxy value of 0.18, and a particle size of 400 nm.

The use of this epoxy resin emulsion:

Component A: This epoxy resin emulsion Component B: BECKOPOX VEH 2188w/55wa

Mix component A: component B = 1:1.2 (equivalent ratio), mix and stir evenly, and apply it on the pre-polished test panel. After the water evaporates, a transparent coating film is formed. The main properties of the coating film are shown in Table 3:

Table 3 embodiment 3 water-based epoxy resin emulsion coating film properties after curing

Claims (6)

1. a non-ion aqueous epoxy resin latex is characterized in that, is made up of the component of following mass percentage content:

Epoxy resin 25%～40%,

Epoxy resin emulsifying agent 13%～20%,

Deionized water 35%～55%,

Epoxide diluent 1%～12%,

Wherein said epoxy resin emulsifying agent is prepared by the component of following mass percentage content:

Epoxy resin 15%～30%,

Mono amino polyethers 25%～60%,

Polyvalent alcohol glycidyl ether 15%～30%,

Organic solvent 5%～20%,

Said epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol f type epoxy resin or novolac epoxy, and wherein oxirane value is 0.1～0.6;

The molecular-weight average of said mono amino polyethers is 500～5000;

The molecular-weight average of said polyvalent alcohol glycidyl ether is 200～10000.

2. according to the said non-ion aqueous epoxy resin latex of claim 1, it is characterized in that said mono amino polyethers is one or more in M-600, M-1000, the M-2070 series.

3. according to the said non-ion aqueous epoxy resin latex of claim 1, it is characterized in that said polyvalent alcohol glycidyl ether is a kind of in polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether or the W 166 triglycidyl ether.

4. according to the said non-ion aqueous epoxy resin latex of claim 1; It is characterized in that said epoxide diluent is one or more of alkyl glycidyl ether, phenyl glycidyl ether or trihydroxymethylpropanyltri diglycidyl ether of butylglycidyl ether, octyl glycidyl ether, carbon 12 to 14.

5. according to the said non-ion aqueous epoxy resin latex of claim 1, it is characterized in that said organic solvent is a kind of in propylene glycol monomethyl ether, propylene-glycol ethyl ether, Ucar 35 butyl ether or the butyl glycol ether.

6. prepare the method for the described a kind of non-ion aqueous epoxy resin latex of one of claim 1～5, it is characterized in that, concrete steps are:

(1) preparation of epoxy resin emulsifying agent: in reaction unit; The epoxy resin and the polyvalent alcohol glycidyl ether that add said ratio; Be warming up to 90 ℃～160 ℃; Drip the mono amino polyethers solution of the said ratio of organic solvent dissolution then, constant temperature continues reaction 2h～5h, airtight preservation after reaction is accomplished;

(2) preparation of aqueous epoxy resin emulsion: epoxy resin emulsifying agent, epoxy resin, the epoxide diluent of (1) preparation is even according to said mixed; Be heated to 40 ℃～50 ℃; Under high speed shear, slowly drip the deionized water of said ratio; Wait to take place to stir 10min～30min after the phase reversion, promptly obtain a kind of non-ion aqueous epoxy resin latex.

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